臺灣博碩士論文加值系統

Calixarenes, 為一種酚和甲醛的環狀聚合物, 因為其具有分子內中空, 故可以嵌合一些小型的有機分子或金屬離子, 而形成 “主-客化合物”, 而這一種特性應可推廣應用於微量檢驗, 離子分離及酵素模擬的研究; 而本論文主要的目的是合成出一系列 1,3-雙烷基醚化的 calix[4]arenes, 並接著利用 ClO2 的氧化特性, 來製備出一系列 1,3-雙烷基醚化的 calix[4]diquinones, 以供進一步的研究和探討。
p-tert-Butylphenol 和甲醛在鹼催化下可聚合成黃綠色之聚合前驅物 26, 此一聚合前驅物於二苯醚 (diphenyl ether) 中迴流可被轉換成 p-tert-butylcalix[4]arene (1); 而此環狀聚合物上的對位三級丁基可再利用三氯化鋁 (AlCl3) 作為催化劑, 以反向的 Friedel-Crafts 反應移除, 而得到對位無取代之 calix[4]arene (7)。
依據文獻報導, calix[4]arene 和多量的鹵化烷類及 K2CO3 在 CH3CN 中迴流, 可得到高產率的 1,3-雙烷基醚化之 calix[4]arenes; 而本論文則採用了碘化乙烷 (iodoethane), 碘化正丙烷 (1-iodopropane), 碘化正丁烷 (1-iodobutane), 溴化甲苯 (benzyl bromide), 和溴化丙烯 (allyl bromide) 等五種鹵化烷類, 來製備出相對應的 25,27-diethyloxy-26,28-dihydroxycalix[4]arene (27)、25,27-dipropyloxy-26,28-dihydroxycalix[4]arene (28)、25,27-dibutyloxy- 26,28-dihydroxycalix[4]arene (29)、25,27-dibenzyloxy-26,28-dihydroxy- calix[4]arene (30) 及 25,27-diallyloxy-26,28-dihydroxycalix[4]arene (31)。
本實驗室曾成功的利用 ClO2 將苯甲酸酯化的 calix[4]arenes 氧化成為相對應的 calix[4]quinones, 本論文亦利用相同的 ClO2 氧化特性, 來對雙烷基醚化之 calix[4]arenes 進行氧化, 其中除乙基醚官能團能經由亞甲基的單鍵向環內作翻轉, 而得到兩種組構異構物 syn-25,27-diethyloxy-26,28-calix[4]diquinone (32) 和anti-25,27- diethyloxy-26,28-calix[4]diquinone (33) 之外, 其餘的氧化反應均只能得到其相對應之 25,27-dipropyloxy-26,28-calix[4]diquinone (34)、25,27-dibutyloxy-26,28-calix[4]diquinone (35)、25,27-dibenzyloxy- 26,28-calix[4]diquinone (36) 及 25,27-diallyloxy-26,28- calix[4]diquinone (37)。
這一些 calix[4]diquinones 的醚類衍生物均可藉由 1H-NMR、13C-NMR、COSY、FAB-MS 及 EA 的分析來鑑定, 並且在本論文中作詳細的敘述和討論。

Calixarenes, which are cyclic oligomers of p-substituted phenols and formaldehyde, are able to include small organic molecules or metal ions within the molecular cavities to form ‘‘ host-guest ’’ complexes. These phenomena have been proposed in the applications of micro- analysis, ion separation, and enzyme-mimic studies. The main purpose of this thesis is to study the oxidative ability of chlorine dioxide toward the calix[4]arene dialkyl ether derivatives.
In the presence of a base, p-tert-butylphenol and formaldehyde were polymerized to form an yellowish precursor 26. Refluxing of this precursor in diphenyl ether for two hours yielded the p-tert- butylcalix[4]arene (1). The p-tert-butyl groups were then removed by AlCl3 catalyzed reverse Friedel-Crafts reaction to give parent calix[4]arene (7).
In the literature reported, calix[4]arenes were dialkylated by refluxing with alkyl halide and potassium corbonate in acetonitrile for 4 hours. Five alkyl halides, iodoethane, 1-iodopropane, 1-iodobutane, benzyl bromide, and allyl bromide, were selected in this thesis, and the corresponding syn-1,3-dialkyloxycalix[4]arenes, 25,27-diethyloxy-26,28- dihydroxycalix[4]arene (27), 25,27-dipropyloxy-26,28-dihydroxy- calix[4]arene (28), 25,27-dibutyloxy-26,28-dihydroxycalix[4]arene (29), 25,27-dibenzyloxy-26,28-dihydroxycalix[4]arene (30), and 25,27- diallyloxy-26,28-dihydroxycalix[4]arene (31), were produced.In the earlier work, calix[4]arene benzoates were oxidized by chlorine dioxide to give calix[4]quinone benzoates. The dialkyloxy calix[4]arenes were subjected to the same chlorine dioxide oxidation. Except for the diethyloxy case, which yielded two stereoisomers syn-25,27-diethyloxy-26,28-calix[4]diquinone (32) and anti-25,27- diethyloxy-26,28-calix[4]diquinone (33), the other dialkyloxy cases yielded the corresponding calix[4]diquinones, 25,27-dipropyloxy-26,28-calix[4]diquinone (34), 25,27-dibutyloxy-26,28-calix[4]diquinone (35), 25,27-dibenzyloxy-26,28-calix[4]diquinone (36), 25,27-diallyloxy-26,28- calix[4]diquinone (37).
All the calix[4]diquinone products were characterized by 1H-NMR, 13C-NMR, COSY, FAB-MS, and EA. The synthetic procedure for calix[4]diquinones were also discussed in this thesis.

第一章 Calixarenes 的簡介
1-1 Calixarenes 的歷史 1
1-2 Calixarenes 的命名 3
第二章 Calixarenes 的應用
2-1 Calixarenes 的組構異構物 6
2-2 Calixarenes 的應用 11
第三章 Calixarenes 的合成
3-1 一步合成法 26
3-2 多步合成法 28
3-3 官能基化法 33
第四章 雙烷基醚化 Calix[4]arenes 的合成
4-1 Calix[4]arenes 的製備 39
4-2 1,3-Dialkoxycalix[4]arenes 的合成 41
4-3 1,3-Dialkoxycalix[4]arenes 的 1H-NMR 光譜 43
第五章 雙烷基醚化 Calix[4]quinones 的合成
5-1 合成 Calix[4]diquinones 之溶劑與溫度的效應 45
5-2 25,27-Diethyloxy-26,28-calix[4]diquinone 的合成
5-3 25,27-Dipropyloxy-26,28-calix[4]diquinone 的合成 49
5-4 25,27-Dibutyloxy-26,28-calix[4]diquinone 的合成50
5-5 25,27-Dibenzyloxy-26,28-calix[4]diquinone 的合成51
5-6 25,27-Diallyloxy-26,28-calix[4]diquinone 的合成52

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